Acetylenic secondary alcohols

ABSTRACT

Novel alkynylcyclopropanecarboxylic acid esters represented by the formula, ##STR1## wherein R 1  represents hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, C 1  -C 4  alkoxy C 1  -C 4  alkyl, C 1  -C 4  alkylthio C 1  -C 4  alkyl, aryl, aryl C 1  -C 4  alkyl, furyl, substituted furyl, thienyl, substituted thienyl, furfuryl, substituted furfuryl, thenyl, substituted thenyl, cyclo C 3  -C 6  alkyl, substituted cyclo C 3  -C 6  alkyl, cyclo C 3  -C 6  alkenyl or substituted cyclo C 3  -C 6  alkenyl; R 2  and R 3  individually represent hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, aryl, aryl C 1  -C 4  alkyl or may form a carbon-carbon bond; or R 1  and R 3  are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom, or R.sub. 1 and R 2  are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom; R 4  represents hydrogen or methyl; R 5  represents hydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1-propenyl, 2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl, 2,2-dichlorovinyl or cyclopentylidenemethyl when R 4  is hydrogen, and R 5  represents methyl when R 4  is methyl; and R 6  and R 7  represent hydrogen or methyl. These novel esters are produced by reacting an alcohol or its halide or arylsulfonate of the formula, ##STR2## wherein R 1 , R 2 , R 3  and R 6  are as defined above, and A is hydroxy, halogen or arylsulfoxy, with a cyclopropanecarboxylic acid of the formula, ##STR3## wherein R 4 , R 5  and R 7  are as defined above, or its reactive derivative. These esters are useful as an insecticide harmless to mammals.

This is a division of application Ser. No. 461,029 filed Apr. 15, 1974,now U.S. Pat. No. 4,003,945.

This invention relates to novel cyclopropanecarboxylic acid esters, aprocess for preparing the said esters, and an insecticidal compositioncontaining the said esters.

More particularly, the invention pertains to novelalkynylcyclopropanecarboxylic acid esters represented by the formula(I). ##STR4## wherein R₁ represents hydrogen, halogen, lower alkylhaving up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms,lower alkynyl having up to 5 carbon atoms, C₁ -C₄ alkoxy C₁ -C₄ alkyl,C₁ -C₄ alkylthio C₁ -C₄ alkyl, aryl, aryl C₁ -C₄ alkyl, furyl,substituted furyl, thienyl, substituted thienyl, furfuryl, substitutedfurfuryl, thenyl, substituted thenyl, cyclo C₃ -C₆ alkyl, substitutedcyclo C₃ -C₆ alkyl, cyclo C₃ -C₆ alkenyl or substituted cyclo C₃ -C₆alkenyl; R₂ and R₃ individually represent hydrogen, halogen, lower alkylhaving up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms,lower alkynyl having up to 5 carbon atoms, aryl, aryl C₁ -C₄ alkyl ormay form a carbon-carbon bond; or R₁ and R₃ are bonded to each other atthe ends to form a polymethylene chain containing or not containing anoxygen or a sulfur atom, or R₁ and R₂ are bonded to each other at theends to form a polymethylene chain containing or not containng an oxygenor a sulfur atom; R₄ represents hydrogen or methyl; R₅ representshydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1-propenyl,2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl,2,2-chlorovinyl or cyclopentylidenemethyl when R₄ is hydrogen, and R₅represents methyl when R₄ is methyl; and R₆ and R₇ represent hydrogen ormethyl.

Various insecticides of the cyclopropanecarboxylic acid ester type haveheretofore been known, and several of such esters are present also inpyrethrum components. Among many insecticides available at present,these pyrethrum components have widely been used for the control ofsanitary injurious insects and agricultural and horticultural injuriousinsects because of their such excellent insecticidal properties thatthey are not only high in insecticidal activity but also low in toxicityto mammals, quick in knock-down effect on injurious insects and scarcelymake the insects resistant thereto. On the other hand, however, they areexpensive and hence have such drawback as being restricted inapplication scope. Heretofore, many attempts have been made by a largenumber of researchers to synthesize various homologous compounds. Theseattempts are directed both to the synthesis of alcohol components of theesters and to the synthesis of acid components.

From such a viewpoint that the above-mentioned drawbacks would beovercome by synthesizing esters having more excellent insecticidaleffects, the present inventors made extensive studies particularly onalcohol coponents of the esters. As a result, the inventors have foundalcohol components which are far more excellent in practicality thanthose in the conventional cyclopropanecarboxylic acid esters.

It is therefore an object of the present invention to provideinsecticides comprising esters containing said alcohol components.

With an aim to investigate to relation between chemical structures andbiological activities of cyclopropanecarboxylic acid ester typeinsecticides, the present inventors attempted the modification of sidechains of α-alkynyl alcohols and examined the insecticidal effects ofesters of said alcohol with various acids. As a result, the inventorshave found that cyclopropanecarboxylic acid esters represented by theaforesaid formula (I) are not only far more prominent in killing effectbut also more quick in knock-down effect on insects, and have confirmedthat the said esters are low in toxicity to mammals and can besynthesized at low costs, and hence can be practically used not only aschemicals for controlling sanitary injurious insects but also aschemicals for controlling insects injurious to agriculture, horticultureand stored cereals. Based on the above finding, the inventors haveaccomplished the present invention.

The cyclopropanecarboxylates of the formula (I) are novel compounds andhave stereoisomers due to the stereo structure and optical isomers dueto the asymmetric carbon atoms, and all of these isomers are within thescope of the invention.

Specific examples of the cyclopropanecarboxylates by the formula (I) areshown in Table 1, but the present invention is not limited thereto:

    __________________________________________________________________________    No. Name                Formula                                               __________________________________________________________________________    1   1-Ethynyl-2-butenyl chrysanthemate                                                                 ##STR5##                                             2   1-Ethynyl-2-methyl-2-butenyl chrysanthemate                                                        ##STR6##                                             3   1-Ethynyl-3-methyl-2-butenyl chrysanthemate                                                        ##STR7##                                             4   1-Ethynyl-2-methyl-2-pentenyl chrysanthemate                                                       ##STR8##                                             5   1-Ethynyl-2-ethyl-2-hexenyl chrysanthemate                                                         ##STR9##                                             6   1-Ethynyl-2,4-hexadienyl chrysanthemate                                                            ##STR10##                                            7   1-Ethynyl-2-isopropyl-2-propenyl chrysanthemate                                                    ##STR11##                                            8   1-Ethynyl-1-(1-cyclohexenyl)- methyl chrysanthemate                                                ##STR12##                                            9   1-Ethynyl-1-(1-cyclopentenyl)methyl 2',2'-dimethyl-3'-(2"-methoxy-            carbonyl-1"-propenyl)cyclopropane- carboxylate                                                     ##STR13##                                            10  1-Ethynyl-1-cyclohexylidene- ethyl 2',2'-dimethyl-3'-(2"- methoxymethy        l-1"-propenyl)- cyclopropanecarboxylate                                                            ##STR14##                                            11  1-Ethynyl-2-methyl-2-butenyl 2',2',3',3'-tetramethylcyclo- propanecarb        oxylate                                                                                            ##STR15##                                            12  1-Ethynyl-2-methyl-2-pentenyl 2',2',3'-trimethylcyclopropane-                 carboxylate                                                                                        ##STR16##                                            13  1-Ethynyl-2-methyl-2-butenyl 2',2'-dimethyl-3'-(1"-propenyl)-                 cyclopropanecarboxylate                                                                            ##STR17##                                            14  1-Ethynyl-2-methyl-2-butenyl 2',2'-dimethyl-3'-(1",3"- butadienyl)cycl        opropane- carboxylate                                                                              ##STR18##                                            15  1-Ethynyl-1-(1-cyclopentenyl)- methyl 2',2'-dimethyl-3'-(2"- methyl-1"        ,3"-butadienyl)- cyclopropanecarboxylate                                                           ##STR19##                                            16  1-Ethynyl-2-methyl-2-butenyl 2',2'-dimethyl-3'-cyclopentyl- idenemethy        lcyclopropane- carboxylate                                                                         ##STR20##                                            17  1-Ethynyl-2-methyl-2-butenyl 1',2',2',3',3'-pentamethyl- cyclopropanec        arboxylate                                                                                         ##STR21##                                            18  1-Ethynyl-2-methyl-2-butenyl 1',2',2'-trimethyl-3'-(2"- methyl-1"-prop        enyl)-cyclo- propanecarboxylate                                                                    ##STR22##                                            19  1-(1-Propynyl)-2-methyl-2-butenyl chrysanthemate                                                   ##STR23##                                            20  1-Ethynyl-2-methyl-2-butenyl 2',2'-dimethyl-3'-(2",2"- dichlorovinyl)c        yclopropane- carboxylate                                                                           ##STR24##                                            21  1-Ethynyl-2-methyl-2-pentenyl 2',2',3',3'-tetramethyl- cyclopropanecar        boxylate                                                                                           ##STR25##                                            22  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-(1"-propenyl)-                cyclopropanecarboxylate                                                                            ##STR26##                                            23  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-vinyl- cyclopropanecar        boxylate                                                                                           ##STR27##                                            24  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-(1",3"- butadienyl)cyc        lopropane- carboxylate                                                                             ##STR28##                                            25  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-(2"- methoxymethyl-1"-        propenyl)- cyclopropanecarboxylate                                                                 ##STR29##                                            26  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-(2"-methoxy- carbonyl-        1"-propenyl)cyclo- propanecarboxylate                                                              ##STR30##                                            27  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-  cyclopropanecarboxylate                             ##STR31##                                            28  1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3'-cyclopentylidene-             methylcyclopropanecarboxylate                                                                      ##STR32##                                            29  1-Ethynyl-2-methyl-2,5-hexadienyl chrysanthemate                                                   ##STR33##                                            30  1-Ethynyl-3-propargylallyl chrysanthemate                                                          ##STR34##                                            31  α-Ethynylcinnamyl chrysanthemate                                                             ##STR35##                                            32  α-Ethynyl-β-methylcinnamyl chrysanthemate                                               ##STR36##                                            33  α-Ethynyl-β-methyl-4- methylcinnamyl chrysanthemate                                     ##STR37##                                            34  α-Ethynyl-β-methyl-2- chlorocinnamyl chrysanthemate                                     ##STR38##                                            35  α-Ethynyl-β-methyl-3,4- methylenedioxycinnamyl chrysanthema        te                                                                                                 ##STR39##                                            36  α-Ethynyl-β-bromocinnamyl chrysanthemate                                                ##STR40##                                            37  α-Ethynyl-β-methyl-3,4- dimethoxycinnamyl chrysanthemate                                ##STR41##                                            38  α-Ethynyl-β-methyl-2,6- dimethyl-4-methoxycinnamyl                 chrysanthemate                                                                                     ##STR42##                                            39  α-Ethynyl-β-methylcinnamyl 2,2,3,3-tetramethyl- cyclopropan        ecarboxylate                                                                                       ##STR43##                                            40  α-Ethynyl-β-methylcinnamyl 2,2-dimethyl-3-cyclopentylidene-         methylcyclopropanecarboxylate                                                                     ##STR44##                                            41  α-Ethynyl-β-methylcinnamyl 2,2-dimethyl-3-(2' -methoxy-            carbonyl-1'-propenyl)-cyclo- propanecarboxylate                                                    ##STR45##                                            42  α-Ethynyl-β-ethyl-4-ethoxy- cinnamyl 2',2',3'-trimethyl-           cyclopropanecarboxylate                                                                            ##STR46##                                            43  α-Ethynyl-β-methyl-3-nitro- cinnamyl 2'2'-dimethyl-3'-             (1"-propenyl)cyclopropane- carboxylate                                                             ##STR47##                                            44  α-Ethynyl-β-methyl-4-dimethyl- aminocinnamyl                       2',2'-dimethyl- 3'-(1",3"-butadienyl)cyclo- propanecarboxylate                                     ##STR48##                                            45  α-Ethynyl-β-methyl-4-cyano- cinnamyl 2',2'-dimethyl-3'-            (2"-methyl-1",3"-butadienyl)- cyclopropanecarboxylate                                              ##STR49##                                            46  α-Ethynyl-β-methyl-4-iso- propylcinnamyl                                                ##STR50##  te                                        47  α-Ethynyl-β-vinylcinnamyl 2,2-dimethyl-3-(2'-methoxymethyl-         1'-propenyl)cyclopropane- carboxylate                                                             ##STR51##                                            48  α-Ethynyl-β-isopropylcinnamyl 2,2,3,3-tetramethylcyclopropa        ne- carboxylate                                                                                    ##STR52##                                            49  α-Ethynyl-β-propargylcinnamyl 2,2-dimethyl-3-(2' -methoxy-         ethyl-1'-propenyl)cyclo- propanecarboxylate                                                        ##STR53##                                            50  α-Ethynyl-β-phenylcinnamyl 2,2,3-trimethylcyclopropane-            carboxylate                                                                                        ##STR54##                                            51  α-Ethynyl-β-benzylcinnamyl 2,2,3,3-tetramethylcyclo-               propanecarboxylate                                                                                 ##STR55##                                            52  α-Ethynyl-γ-phenylcinnamyl 2,2-dimethyl-3-(1'-propenyl)-          cyclopropanecarboxylate                                                                            ##STR56##                                            53  α-Ethynyl-γ-methylcinnamyl chrysanthemate                                              ##STR57##                                            54  α-Ethynyl-β-methylcinnamyl 1,2,2-trimethyl-3-(2'-methyl-           1'-propenyl)cyclopropane-  carboxylate                                                             ##STR58##                                            55  α-Ethynyl-β-methyl-2-methyl- cinnamyl 1',2',2'-trimethyl-3'        - cyclopentylidenemethyl- cyclopropanecarboxylate                                                  ##STR59##                                            56  α-Ethynyl-β-chlorocinnamyl 1,2,2,3,3-pentamethyl- cycloprop        anecarboxylate                                                                                     ##STR60##                                            57  α-Ethynyl-β-methyl-3,4- methylendioxycinnamyl 1',2',2'-trim        ethyl-3'-(2"- methoxycarbonyl-1"-propenyl)- cyclopropanecarboxylate                                ##STR61##                                            58  α-(1-Propynyl)-β-methyl- cinnamyl chrysanthemate                                        ##STR62##                                            59  α-Ethynyl-β-methylcinnamyl 2,2-dimethyl-3-(2',2'-dichloro-         inyl)cyclopropanecarboxylate                                                                       ##STR63##                                            60  α-Ethynyl-γ-(2-furyl)-allyl chrysanthemate                                             ##STR64##                                            61  α-Ethynyl-γ-(2-thienyl)- allyl chrysanthemate                                          ##STR65##                                            62  α-Ethynyl-γ-benzylallyl chrysanthemate                                                 ##STR66##                                            63  α-Ethynyl-β-ethylcinnamyl chrysanthemate                                                ##STR67##                                            64  1-Ethynyl-2-butyl-1-yl chrysanthemate                                                              ##STR68##                                            65  1-Ethynyl-2-pentyn-1-yl chrysanthemate                                                             ##STR69##                                            66  1-Ethynyl-2-hexyn-1-yl chrysanthemate                                                              ##STR70##                                            67  1-Ethynyl-2-heptyn-1-yl chrysanthemate                                                             ##STR71##                                            68  1-Ethynyl-4-methoxy-2-butyn-1-yl chrysanthemate                                                    ##STR72##                                            69   1-Ethynyl-5-methoxy-2-pentyn-1-yl chrysanthemate                                                  ##STR73##                                            70  1-Ethynyl-4-ethoxy-2-butyn-1-yl chrysanthemate                                                     ##STR74##                                            71  1-Ethynylhexa-2-yn-5-en-1-yl chrysanthemate                                                        ##STR75##                                            72  1-Ethynylhexa-2,5-diyn-1-yl chrysanthemate                                                         ##STR76##                                            73  1-Ethynylhepta-2-yn-6-en-1-yl chrysanthemate                                                       ##STR77##                                            74  1-Ethynylhepta-2,6-diyn-1-yl chrysanthemate                                                        ##STR78##                                            75  1-Ethynyl-6-chloro-hexa-2-yn-5- en-1-yl chrysanthemate                                             ##STR79##                                            76  1-Ethynyl-4-phenyl-2-butyn-1-yl chrysanthemate                                                     ##STR80##                                            77  1-Ethynyl-5-phenyl-2-pentyn-1-yl chrysanthemate                                                    ##STR81##                                            78  1-Ethynyl-6-phenyl-2-hexyn-1-yl chrysanthemate                                                     ##STR82##                                            79  1-Ethynyl-4-phenoxy-2-butyn-1-yl chrysanthemate                                                    ##STR83##                                            80  1-Ethynyl-4-phenylthio-2-butyn- 1-yl chrysanthemate                                                ##STR84##                                            81  1-Ethynyl-3-phenyl-2-propyn-1-yl chrysanthemate                                                    ##STR85##                                            82  1-(1'-Propynyl)-hexa-2-yn-5- en-1-yl chrysanthemate                                                ##STR86##                                            83  1-Ethynyl-4-(3',4'-methylene- dioxyphenyl)-2-butyn-1-yl chrysanthemate                             ##STR87##                                            84  1-Ethynyl-2-hexyn-1-yl 2',2',3',3'-tetramethyl- cyclopropanecarboxylat        e                                                                                                  ##STR88##                                            85  1-Ethynyl-2-heptyn-1-yl 2',2',3',3'-tetramethylcyclo- propanecarboxyla        te                                                                                                 ##STR89##                                            86  1-Ethynylhexa-2-yn-5-en-1-yl 2',2',3',3'-tetramethyl- cyclopropanecarb        oxylate                                                                                            ##STR90##                                            87  1-Ethynyl-4-phenyl-2-butyn-1-yl 2',2',3',3'-tetramethyl- cyclopropanec        arboxylate                                                                                         ##STR91##                                            88  1-Ethynyl-4-phenoxy-2-butyn-1- yl 2',2',3',3'-tetramethyl- cyclopropan        ecarboxylate                                                                                       ##STR92##                                            89  1-Ethynylhexa-2-yn-5-en-1-yl 2',2',3'-trimethylcyclopropane- carboxyla        te                                                                                                 ##STR93##                                            90  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(2"-methyl- 1",3"-butad        ienyl)cyclopropane- carboxylate                                                                    ##STR94##                                            91  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(1"- propenyl)cycloprop        ane- carboxylate                                                                                   ##STR95##                                            92  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(1",3"- butadienyl)cycl        opropane- carboxylate                                                                              ##STR96##                                            93  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethylcyclopropane- carboxylate                               ##STR97##                                            94  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-cyclopentylidene-              methylcyclopropanecarboxylate                                                                      ##STR98##                                            95  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(2",2"- dichlorovinyl)c        yclopropane- carboxylate                                                                           ##STR99##                                            96  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(2"-methoxy- carbonyl-1        "-propenyl)- cyclopropanecarboxylate                                                               ##STR100##                                           97  1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-(2"- methoxymethyl-1"-p        ropenyl)- cyclopropanecarboxylate                                                                  ##STR101##                                           98  1-Ethynylhexa-2-yn-5-en-1-yl 1',2',2',3',3'-pentamethyl- cyclopropanec        arboxylate                                                                                         ##STR102##                                           99  1-Ethynylhexa-2-yn-5-en-1-yl 1',2',2'-trimethyl-3'-(2"- methyl-1"-prop        enyl)cyclo- propanecarboxylate                                                                     ##STR103##                                           100 1-Ethynylhexa-2-yn-5-en-1-yl 1',2',2'-trimethyl-3'- cyclopentylideneme        thyl- cyclopropanecarboxylate                                                                      ##STR104##                                           101 1-Ethynylhexa-2-yn-5-en-1-yl 2',2'-dimethyl-3'-vinyl- cyclopropanecarb        oxylate                                                                                            ##STR105##                                           102 1-Ethynyl-3-(2'-cyclopentenyl)- allyl chrysanthemate                                               ##STR106##                                           103 1-Ethynyl-4-methylcyclopentenyl)- 2-butenyl chrysanthemate                                         ##STR107##                                           104 1-Ethynyl-2-methyl-3-(1'- cyclopentenyl)allyl 2",2",3",3"- tetramethyl        cyclopropane- carboxylate                                                                          ##STR108##                                           105 1-Ethynyl-2-methyl-3-(2'- cyclopentenyl)allyl chrysanthemate                                       ##STR109##                                           106 1-Ethynyl-3-cyclopentylallyl chrysanthemate                                                        ##STR110##                                           107 1-Ethynyl-3-(3'-cyclopentenyl)- allyl 2",2"-dimethyl-3"- (1"',3"'-buta        dienyl)cyclo- propanecarboxylate                                                                   ##STR111##                                           108 1-Ethynyl-2-ethyl-3-(1'- cyclopentenyl)allyl chrysanthemate                                        ##STR112##                                           109 1-Ethynyl-2-ethyl-3-(1'- cyclopentenyl)allyl chrysanthemate                                        ##STR113##                                           110 1-Ethynyl-2-methyl-3-(2'- cyclopentenyl)allyl 2",2"- dimethyl-3"-(1"'-        propenyl)- cyclopropanecarboxylate                                                                 ##STR114##                                           111 1-Ethynyl-2-methyl-4-(1'- cyclopentenyl)-2-butenyl 2",2"- dimethyl-3"-        cyclopentylidene- methylcyclopropanecarboxylate                                                    ##STR115##                                           112 1-Ethynyl-4-(4'-oxa-1'- cyclopentenyl)-2-butenyl chrysanthemate                                    ##STR116##                                           113 1-Ethynyl-2-methyl-3- cyclohexylallyl chrysanthemate                                               ##STR117##                                           114 1-Ethynyl-2-methyl-3- (3'-cyclohexenyl)allyl chrysanthemate                                        ##STR118##                                           115 1-Ethynyl-3-(3'-cyclohexenyl)- allyl 2",2"-dimethyl-3"-(1"'- propenyl)        cyclopropanecarboxylate                                                                            ##STR119##                                           116 1-Ethynyl-3-(2'-cyclohexenyl)- allyl 2",2",3",3"-tetramethyl-                 cyclopropanecarboxylate                                                                            ##STR120##                                           117 1-Ethynyl-4-(1'-cyclohexenyl)- 2-butenyl 2",2",3"-trimethyl-  cyclopro        panecarboxylate                                                                                    ##STR121##                                           118 1-Ethynyl-2-methyl-3-(3'- cyclohexenyl)allyl 2",2"-dimethyl- cycloprop        anecarboxylate                                                                                     ##STR122##                                           119 1-Ethynyl-2-methyl-4-(2'- cyclohexenyl)-2-butenyl chrysanthemate                                   ##STR123##                                           120 1-Ethynyl-3-(3'-cyclohexenyl)- allyl 2",2"-dimethyl-3"- (2"',2"'-dichl        orovinyl)- cyclopropanecarboxylate                                                                 ##STR124##                                           121 1-Ethynyl-2-methyl-3-(3'- cyclohexenyl)allyl 2",2"- dimethyl-3"-cyclop        entylidene- methylcyclopropanecarboxylate                                                          ##STR125##                                           122 1-Ethynyl-2-methyl-3-(2'- oxa-3'-cyclohexenyl)allyl 2",2"-dimethyl-3"-        (1"',3"'- butadienyl)cyclopropane- carboxylate                                                     ##STR126##                                           123 1-Ethynyl-3-(5'-oxa-3'- cyclohexenyl)allyl chrysanthemate                                          ##STR127##                                           124 1-Ethynyl-2-ethyl-3-(2'-oxa- 3'-cyclohexenyl)allyl 2",2"-dimethyl-3"-(        1"'- propenyl)cyclopropanecarboxylate                                                              ##STR128##                                           125 1-Ethynyl-2-methyl-3-(2'- oxacyclohexyl)allyl chrysanthemate                                       ##STR129##                                           126 1-Ethynyl-2-methyl-2-pentenyl 2',2'-dimethyl-3-(2",2"-dichlorovinyl)-         yclopropanecarboxylate                                                                             ##STR130##                                           127 1-Ethynyl-2-methyl-2,5-hexadien- 1-yl 2',2'-dimethyl-3'-(2",2"-di-            chlorovinyl)-cycopropane- carboxylate                                                              ##STR131##                                           128 1-Ethynyl-2-methyl-2,6- heptadien-1-yl chrysanthemate                                              ##STR132##                                           129 1-Ethynyl-2-methyl-2,6- heptadien-1-yl 2',2'-dimethyl-3'- 2",2"-dichlo        rovinyl-cyclopropane- carboxylate                                                                  ##STR133##                                           130 1-Ethynyl-2-methyl-2-butenyl 2',2'-dimethyl-3'-(2",2"-dichlorovinyl)-         yclopropanecarboxylate                                                                             ##STR134##                                           131 α-Ethynyl-γ-benzylallyl 2',2'- dimethyl-3'-2",2"-dichlorov        inyl)- cyclopropanecarboxylate                                                                     ##STR135##                                           132 α-Ethynylcinnamyl 2',2'- dimethyl-3'-(2",2"-dichlorovinyl)-             cyclopropanecarboxylate                                                                            ##STR136##                                           133 α-Ethynylcinnamyl 2',2'- dimethyl-3'-cyclopentylidene- methyl-cy        clopropanecarboxylate                                                                              ##STR137##                                           134 α-Ethynylcinnamyl 2',2'-dimethyl-3'-(2"-methoxy- methyl-1'-prope        nyl)cyclo- propanecarboxylate                                                                      ##STR138##                                           135 α-Ethynyl-β-bromocinnamyl 2',2'-dimethyl-3'-3'-(2",2"-di-          chlorovinyl)-cyclopropane- carboxylate                                                             ##STR139##                                           136 α-Ethynyl-β-methyl- 2,6-dimethyl-4-methoxycinnamyl                 2',2'-dimethyl-3'-(2",2"-dichlorovinyl)- cyclopropane-carboxylate                                  ##STR140##                                           137 α-Ethynyl-β-methyl-4-cyanocinnamyl 2',2'-dimethyl-3'-(2",2"        -dichlorovinyl)- cyclopropane-carboxylate                                                          ##STR141##                                           138 α-Ethynyl-γ-phenylcinnamyl 2,2-dimethyl-3-(2',2'-dichloro-         vinyl)-cyclopropane carboxylate                                                                   ##STR142##                                           139 α-Ethynyl-β-methyl-3,4- methylenedioxy-cinnamyl 2',2'-dimet        hyl-3'-(2",2"-dichlorovinyl)- cyclopropane carboxylate                                             ##STR143##                                           140 α-Ethynyl-γ-(2-furyl)allyl 2',2'-dimethyl-3'-(2",2"-dichlo        ro- vinyl)-cyclopropanecarboxylate                                                                 ##STR144##                                           141 α-Ethynyl-β-ethylcinnamyl 2,2-dimethyl-3-(2',2'-di-                chlorovinyl)-cyclopropane- carboxylate                                                             ##STR145##                                           142 1-Ethynyl-4-methoxy-2-butyn- 1-yl 2',2'-dimethyl-3'-(2",2"- dichlorovi        nyl)-cyclopropane- carboxylate                                                                     ##STR146##                                           143 1-Ethynyl-4-vinyl-2-butyn-1-yl 2',2'-dimethyl-3'-(2",2"-dichloro-             vinyl)-cyclopropanecarboxylate                                                                     ##STR147##                                           144 1-Ethynyl-4-phenoxy-2-butyn-1-yl 2',2'-dimethyl-3'-(2",2"-dichloroviny        l)- cyclopropanecarboxylate                                                                        ##STR148##                                           145 1-Ethynyl-3-propargylallyl 2',2'-dimethyl-3'-(2",2"-dichloro-                 vinyl)-cyclopropanecarboxylate                                                                     ##STR149##                                           146 1-Ethynyl-2-methyl-3-propargyl- allyl chrysanthemate                                               ##STR150##                                           147 1-Ethynyl-3-methyl-3-propargyl- allyl 2',2'-dimethyl-3'-(2",2"-               dichlorovinyl)-cyclopropane- carboxylate                                                           ##STR151##                                           148 1-Ethynyl-2-methyl-hepta- 2-en-6-yn-1-yl chrysanthemate                                            ##STR152##                                           149 1-Ethynyl-2-methyl-hepta-2-en- 6-yn-1-yl 2',2'-dimethyl-3'-(2",2"-            dichlorovinyl)-cyclopropane- carboxylate                                                           ##STR153##                                           150 1-Ethynyl-hepta-2-en-6-yn- 1-yl chrysanthemate                                                     ##STR154##                                           151 1-Ethynyl-2-methyl-3-benzylallyl 2',2'-dimethyl-3'-(2",2"-dichloroviny        l)- cyclopropanecarboxylate                                                                        ##STR155##                                           152 1-Ethynyl-2-methyl-3-benzylallyl chrysanthemate                                                    ##STR156##                                           __________________________________________________________________________

The esters represented by the aforesaid formula (I) can be obtained byreacting an alcohol, its halide or arylsulfonate, of the formula (II),##STR157## wherein R₁, R₂, R₃ and R₆ are as defined above; and A is ahydroxy group, a halogen atom or an arylsulfoxy group, with acyclopropanecarboxylic acid, or its reactive derivative, of the formula(III), ##STR158## wherein R₄, R₅ and R₇ are as defined above, ifnecessary, in the presence of a suitable reaction auxiliary reagent.

The reactive derivative of cyclopropanecarboxylic acid which is referredto herein include acid halides, acid anhydrides, lower alkyl esters andsalts.

Procedures for synthesizing the esters according to the presentinvention are explained in more detail below.

In case an alcohol of the formula (II) (A is a hydroxy group) and acarboxylic acid of the formula (III) are used, the reaction is carriedout under dehydration conditions. Thus, the alcohol is reacted at roomtemperature or at an elevated temperature with the carboxylic acid in asuitable inert solvent in the presence of a dehydrating agent such asdicyclohexylcarbodiimide where by a desired ester can be obtained in ahigh yield.

In case an acid halide is used as a reactive derivative of thecarboxylic acid of the general formula (III), the reaction can besufficiently accomplished at room temperature by reacting the acidhalide with an alcohol of the formula (II) (A is a hydroxy group), usingas a hydrogen halide-removing reagent such an organic tertiary base aspyridine, triethylamine or the like. The acid halide used in this casemay be any of the halides within the scope of the present invention, butis ordinarily an acid chloride. In the reaction, the use of a solvent isdesirable for smooth progress of the reaction, and such an inert solventas benzene, toluene or petroleum benzine is ordinarily used.

In case an acid anhydride is used as a reactive derivative of thecarboxylic acid of the formula (III), no auxiliary agent is particularlyrequired, and the object can be accomplished by reacting the acidanhydride with an alcohol of the formula (II) (A is a hydroxy group). Inthis case, the elevation of temperature is preferable for accelerationof the reaction, and the use of an inert solvent such as toluene orxylene is preferable for smooth progress of the reaction, though notalways indispensable.

In case a lower alkyl ester is used as a reactive derivative of thecarboxylic acid of the formula (III), the reaction is accomplished byreacting said ester with an alcohol of the formula (II) (A is a hydroxygroup) at an elevated temperature in the presence of such a basiccatalyst as sodium alkoxide, while removing out of the system a lowboiling alcohol formed in the reaction. The use of such an inert solventbenzene, toluene or the like is preferable for smooth progress of thereaction. The lower alkyl ester of carboxylic acid used in this case ispreferably methyl ester, ethyl ester, n-propyl ester, isopropyl ester orn-butyl ester.

In case an ester of the formula (I) is desired to be obtained by use ofa halide of the alcohol of the formula (II) (A is a halide), thecarboxylic acid of the formula (III), which is the other reactant, maybe used in the form of an alkali metal salt or a salt of an organictertiary base, or an organic tertiary base may be added, at the time ofreaction, together with the carboxylic acid. In this case, it isdesirable for smooth progress of the reaction that an inert solvent suchas benzene or acetone is used and the system is heated to the boilingpoint of the solvent or to a temperature near the boiling point thereof.The halide of alcohol used in the above case is ordinarily in the formof chloride, but may be any other halide such as bromide or the like.

In the case where an ester of the formula (I) is desired to be obtainedby use of an arylsulfonate of the alcohol of the formula (II), the otherreactant and the reaction conditions are the same as in the case wherethe above-mentioned halide of alcohol is used. As the arylsulfonate, atosylate is frequently used, in general.

The present invention will be more particularly illustrated by thefollowing Examples which should not restrict the invention defined inthe attached claims.

Production of the esters represented by the formula (I)

The esters shown in Table I were produced by standard processes eachrepresented by A, B, C, D, E and F as follows:

Process A

A reaction of an alcohol with a carboxylic acid halide

0.05 Mol of an alcohol was dissolved in three times the volume of drybenzene. 0.075 Mol of pyridine was added to the solution. On the otherhand, 0.053 mol of a carboxylic acid chloride was dissolved in threetimes the volume of dry benzene. The solution thus obtained was added ata time to the above-mentioned solution, whereupon and exothermicreaction occurred. After the solution had been allowed to standovernight in a tightly sealed vessel, a small amount of water was addedto dissolve pyridine hydrochloride precipitated. The aqueous layer wasseparated and the organic layer was then washed with 5% aqueoushydrochloric acid, a saturated aqueous solution of sodium bicarbonateand a saturated aqueous salt solution successively. After the organiclayer had been dried an anhydrous sodium sulfate, the benzene solutionwas stirred with neutral alumina for 30 minutes to decolorize andfiltered off, and then the benzene was removed by distillation to obtainthe final product.

Process B

A reaction (dehydration) between an alcohol and a carboylic acid.

A solution of 0.05 mol of an alcohol in three times the volume ofbenzene was mixed with a solution of 0.05 mol of a carboxylic acid inthree times the volume of benzene. 0.08 Mol of dicyclohexylcabodiimidewas added thereto. After the mixture had been allowed to stand overnightin a tightly sealed vessel, the mixture was refluxed for two hours tocomplete the reaction and then cooled. Afterdicyclohexylcarbodiimidourea precipitated was filtered off, the sameafter-treatment as in the standard operational method A was then carriedout to obtain the final product.

Process C

A reaction of an alcohol with a carboxylic acid anhydride.

0.05 Mol of an alcohol was dissolved in three times the volume oftoluene. 0.05 Mol of a carboxylic acid anhydride synthesized from thecorresponding carboxylic acid and acetic anhydride was added thereto.The mixture was then reacted for three hours at 100° C. The reactionmixture was cooled and a 5% aqueous solution of sodium hydroxide wasadded to neutralize the mixture. Excess of the acid anhydride and thecarboxylic acid formed by the reaction were recovered in the form ofsodium salt. The after-treatment of the organic layer was then carriedout in the same manner as in the standard operational method A to obtainthe desired ester.

Process D

A transesterification between an alcohol and a lower alkyl carboxylate

0.05 Mol of an alcohol and 0.06 mol of an ethyl carboxylate weredissolved in five times the volume of dry toluene. 2 Grams of sodiumethoxide was added. The mixture was then refluxed with well stirring for10 hours to complete the reaction. Cold water was carefully added andthe mixture was separated into an aqueous layer and an organic layer.The after-treatment was then carried out in the same manner as in thestandard operational method A to obtain the final product.

Process E

A reaction of a halide compound with a carboxylic acid

0.05 Mol of a halide compound and 0.06 mol of a carboxylic acid weredissolved in three times the volume of acetone. The solution was warmedat 15° to 20° C. A solution of 0.08 mol of triethylamine in three timesthe volume of acetone was dropped into the above solution with stirringin one hour. The mixture was then refluxed for two hours to complete thereaction. After the reaction mixture had been cooled, the triethylaminehydrochloride separated was filtered off and the acetone was removedfrom the filtrate by distillation. Three times the volume of benzene wasadded to the remaining liquid and the after-treatment of the liquid wascarried out in the same manner as in the standard operational method Ato obtain the desired ester.

Process F

A reaction of the arylsulfonate of an alcohol with a carboxylate

0.05 Mol of an arylsulfonate was dissolved in three times the volume ofacetone. 0.06 Mol of sodium carboxylate, synthesized by reacting thecorresponding carboxylic acid with an equimolar amount of sodiumhydroxide in water and distilling off the water and evaporating theresidue to dryness, was added at room temperature with well stirring in30 minutes. The mixture was then refluxed for 30 minutes to complete thereaction. After the mixture had been cooled, the solid matter separatedwas removed by filtration and the acetone was removed from the filtrateby distillation. The residue was dissolved in three times the volume ofbenzene. The after-treatment of the solution was then carried out in thesame manner as in the standard operational method A to obtain the finalproduct.

Typical examples of cyclopropanecarboxylic acids of the formula (III)which are used in the present invention are as shown below, whichinclude cis and trans isomers and optically active acids according todouble bond and/or asymetric carbon atoms.

And reactive derivatives of these carboxylic acids are easily preparedfrom the corresponding carboxylic acid by such a known method as usedfor chrysanthemic acid.

2,2-Dimethylcyclopropanecarboxylic acid

2,2,3-Trimethylcyclopropanecarboxylic acid

2,2,3,3-Tetramethylcyclopropanecarboxylic acid

2,2-Dimethyl-3-(2'-methyl-1'-propenyl)-cyclopropanecarboxylic acid

2,2-Dimethyl-3-vinylcyclopropanecarboxylic acid

2,2-Dimethyl-3-(1'-propenyl)cyclopropanecarboxylic acid

2,2-Dimethyl-3-(1',3'-butadienyl)cyclopropanecarboxylic acid

2,2-Dimethyl-3-(2'-methyl-1',3'-butadienyl)cyclopropanecarboxylic acid

2,2-Dimethyl-3-(2',2'-dichlorovinyl)cyclopropanecarboxylic acid

2,2-Dimethyl-3-cyclopentylidenemethyl-cyclopropanecarboxylic acid

2,2-Dimethyl-3-(2'-methoxycarbonyl-1'-propenyl)cyclopropanecarboxylicacid

2,2-Dimethyl-3-(2'-methoxymethyl-1'-propenyl) cyclopropanecarboxylicacid

1,2,2,3,3-Pentamethylcyclopropanecarboxylic acid

1,2,2-Trimethyl-3-(2'-methyl-1'-propenyl)cyclopropanecarboxylic acid

1,2,2-Trimethyl-3-(2-methoxycarbonyl-1'- propenyl)cyclopropanecarboxylicacid

1,2,2-Trimethyl-3-cyclopentylidinemethylcyclopanecarboxylic acid

Typical examples of α-alkynyl alcohols of the formula (II) which areused in the present invention are as shown below.

Halides are prepared by halogenating the alcohols with thionyl halidesor phosphorus halides, and arylsulfonate prepared by treating alcoholswith arylsulfochloride.

1-Ethynyl-2-butenyl alcohol

1-Ethynyl-2-methyl-2-butenyl alcohol

1-Ethynyl-3-methyl-2-butenyl alcohol

1-Ethynyl-2-methyl-2-pentenyl alcohol

1-Ethynyl-2-ethyl-2-hexenyl alcohol

1-Ethynyl-2,5-hexadienyl alcohol

1-Ethynyl-2-isopropylallyl alcohol

1-(1'-Propynyl)-2-methyl-2-butenyl alcohol

1-Ethynyl-1-(1-cyclohexenyl)methyl alcohol

1-Ethynyl-1-(1'-cyclopentenyl)methyl alcohol

1-Ethynyl-1-cyclohexylidenemethyl alcohol

1-Ethynyl-3-propargylallyl alcohol

1-Ethynyl-2-methyl-3-propargylallyl alcohol

α-Ethynylcinnamyl alcohol

α-Ethynyl-β-methylcinnamyl alcohol

α-Ethynyl-β-methyl-4-methylcinnamyl alcohol

α-Ethynyl-β-methyl-2-chlorocinnamyl alcohol

α-Ethynyl-β-methyl-3,4-methylenedioxycinnamyl alcohol

α-Ethynyl-β-methyl-3-nitrocinnamyl alcohol

α-Ethynyl-β-methyl-4-dimethylaminocinnamyl alcohol

α-Ethynyl-β-methyl-4-cyanocinnamyl alcohol

α-Ethynyl-β-methyl-4-isopropylcinnamyl alcohol

α-Ethynyl-β-ethyl-4-ethoxycinnamyl alcohol

α-Ethynyl-β-methyl-3,4-dimethoxycinnamyl alcohol

α-Ethynyl-β-methyl-2,6-dimethyl-4-methoxycinnamyl alcohol

α-Ethynyl-β-bromocinnamyl alcohol

α-Ethynyl-β-vinylcinnamyl alcohol

α-Ethynyl-β-isopropylcinnamyl alcohol

α-Ethynyl-β-propargylcinnamyl alcohol

α-Ethynyl-β-phenylcinnamyl alcohol

α-Ethynyl-β-benzylcinnamyl alcohol

α-Ethynyl-γ-phenylcinnamyl alcohol

α-Ethynyl-γ-methylcinnamyl alcohol

α-(1-Propynyl)-β-methylcinnamyl alcohol

α-Ethynyl-γ-(2-furyl)allyl alcohol

α-Ethynyl-γ-(2-thienyl)allyl alcohol

α-Ethynyl-γ-benzylallyl alcohol

1-Ethynyl-2-butyn-1-ol

1-Ethynyl-2-pentyn-1-ol

1-Ethynyl-2-hexyn-1-ol

1-Ethynyl-2-heptyn-1-ol

1-Ethynyl-4-methoxy-2-butyn-1-ol

1-Ethynyl-5-methoxy-2-pentyn-1-ol

1-Ethynyl-4-ethoxy-2-butyn-1-ol

1-Ethynylhexa-2-yn-5-en-1-ol

1-Ethynylhexa-2,5-diyn-1-ol

1-Ethynylhepta-2-yn-6-en-1-ol

1-Ethynylhepta-2,6-diyn-1-ol

1-Ethynyl-6-chloro-2-yn-5-en-1-ol

1-Ethynyl-4-phenyl-2-butyn-1-ol

1-Ethynyl-5-phenyl-2-pentyn-1-ol

1-Ethynyl-6-phenyl-2-hexyn-1-ol

1-Ethynyl-4-phenylthio-2-butyn-1-ol

1-Ethynyl-3-(3'-methylphenyl)-2-propyn-1-ol

1-(1'-Propynyl)-4-(3",4"-methylenedioxyphenyl)-2-butyn-1-ol

1-Ethynyl-3-(2'-cyclopentenyl)allyl alcohol

1-Ethynyl-2-methyl-3-(1'-cyclopentyl)allyl alcohol

1-Ethynyl-3-cyclopentylallyl alcohol

1-Ethynyl-2-ethyl-3-(1'-cyclopentenyl)allyl alcohol

1-Ethynyl-2-methyl-3-(2'-cyclopentenyl)allyl alcohol

1-Ethynyl-4-(1'-cyclopentenyl)-2-butenyl alcohol

1-Ethynyl-3-(3'-cyclopentenyl)allyl alcohol

1-Ethynyl-2-methyl-4-(1'-cyclopentenyl)-2-butenyl alcohol

1-Ethynyl-4-(4'-oxa-1'-cyclopentenyl)-2-butenyl alcohol

1-Ethynyl-2-methyl-3-cyclohexylallyl alcohol

1-Ethynyl-3-(3'-cyclohexenyl)allyl alcohol

1-Ethynyl-4-(1'-cyclohexenyl)-2-butenyl alcohol

1-Ethynyl-4-(2'-cyclohexenyl)-2-butenyl alcohol

1-Ethynyl-2-methyl-3-(3'-cyclohexenyl)allyl alcohol

1-Ethynyl-3-(2'-cyclohexenyl)allyl alcohol

1-Ethynyl-2-methyl-3-(2'-oxo-3'-cyclohexenyl)allyl alcohol

1-Ethynyl-3-(5'-oxa-3'-cyclohexenyl)allyl alcohol

1-Ethynyl-2-ethyl-3-(2'-oxa-3'-cyclohexenyl)allyl alcohol

1-Ethynyl-2-methyl-3-(2'-oxacyclohexyl)allyl alcohol

The alkynyl alcohol represented by the formula (II) is a novel compound,and may be prepared easily according to the following processes.

The processes which comprise reacting an aldehyde compound representedby the formula (IV) with the ethynyl compound represented by the formula(V) or a Grignard reagent represented by the formula (IV) are asfollows: ##STR159## wherein R₁, R₂, R₃ and R₆ are as defined above, Mrepresents an alkali metal (ex. lithium, sodium, potassium) and Xrepresents a chlorine or a bromine atom.

Of the above-mentioned starting materials, the compound represented bythe formula (IV) may be prepared easily according to the followingprocesses;

(1) The process which comprises reacting a carbonyl compound of theformula (VII), ##STR160## wherein R₁ and R₂ are as defined above, withan aldehyde compound of the formula (VIII),

    R.sub.3 --CH.sub.2 --CHO                                   (VIII)

wherein R₃ is as defined above, by aldol condensation reaction.

(2) The process which comprises reducing and α,β-unsaturated ester ofthe formula (IX), ##STR161## wherein R₁, R₂ and R₃ are as defined above,and R is lower alkyl having up to 5 carbon atoms and further oxidizing,or

(3) The process which comprises reducing an alcohol compound of theformula (X),

    R.sub.1 --C.tbd.C--CH.sub.2 OH                             (X)

wherein R₁ is as defined above with, for example, lithium aluminumhydride to form the alcohol of the formula (XI), ##STR162## and furtheroxidizing the said alcohol compound (XI).

On the other hand, the starting material of the formula (IV) may beprepared easily according to the following process:

The process which comprises oxidizing an alcohol compound of the formula(X),

    R.sub.1 --C.tbd.C--CH.sub.2 OH

wherein R₁ is as defined above.

Practical embodiments for preparing the starting materials areillustratively shown in the following reference examples, but are notlimited thereto.

REFERENCE EXAMPLE 1

To a solution of ethynyl magnesium bromide (prepared from 2.91 g ofmagnesium) in 100 ml of tetrahydrofuran, was added dropwise 9.8 g of2-methylpenta-2-en-1-al at a temperature from 0° C. to 10° C. undercooling with ice-bath. The resulting reaction solution was stirred for 3hours at room temperature to complete the reaction and then the reactionsolution was poured into a saturated ammonium chloride solution with 50g of ice. After stirring, the solution was extracted twice with 100 mlof ether and the organic layers were combined, and then washed with 50ml of a saturated sodium chloride solution. After the organic layer hadbeen dried over anhydrous sodium sulfate, the ether was evaporated. Theremaining liquid was purified by distillation at reduced pressure toobtain 10.2 g of a colorless oil, b.p. 85°-88° C./20 mm Hg.

REFERENCE EXAMPLE 2

To a solution of ethynyl magnesium bromide (prepared from 2.91 g ofmagnesium) in 100 ml of tetrahydrofuran, was added dropwise 11.0 g of2-methyl-hexa-2,5-diene-1-al at a temperature from 0° C. to 10° C. undercooling with ice-bath. The resulting reaction solution was stirred for 3hours to complete the reaction and the same after-treatment as in theReference Example 1 was then carried out to obtain 12.3 g of a colorlessoil, b.p. 60°-65° C./7 mm Hg.

The esters of the present invention find broad uses for the preventionof epidemics and for the control of insects injurious to stored cereals.Furthermore, they are extremely useful for the control of agriculturaland forestry injurious insects such as green rice leaf-hoppers, smallerbrown planthoppers, rice steam borers, larvae of Japanese giant silkmoth, common cabbage-worms, cabbage army worms, diamond back moth, cutworms, tent catapillar, etc. Particularly, they are low toxic andharmless to mammals, and hence are freely applicable to crops beforeharvest, foods and packaging materials, and are usable for control ofinsects injurious to stored cereals and for home horticulture and greenhouse cultivation.

The cyclopropanecarboxylic acid esters of the formula (I), which areexemplified by the above-mentioned compounds, are more excellent ininsecticidal effect and knock-down effect than the known chrysanthemicacid esters. In order to make the above fact clearer, comparison ineffectiveness between typical compounds of the present invention andallethrin is shown below with reference to Test Examples. Othercompounds of the formula (I) and their geometrical isomers and opticalisomers display excellent effects as well.

TEST EXAMPLE 1

0.6% Mosquito coils of each compounds (Compounds No. 1, 2, 4, 6, 11, 12,21, 71 and its isomers, 86, 89, 90, 91, 92, allethrin) were prepared ina similar manner as in Examples P, Q or R.

Into a (70 cm)³ glass chamber were liberated each of 20 adults per groupof Northern house mosquitoes and 20 adults per group of houseflies. Inthe case of the Northern house mosquitoes, 1 g of each of the mosquitocoils, and in the case of the houseflies, 1 g of each of the mosquitocoils, were individually ignited on both ends and placed at the centerof the chamber. Thereafter, the number of knocked down insects wascounted to calculate 50% knock-down times (KT₅₀).

The results obtained from several repetition were as shown in Tables 2aand 2b.

                  TABLE 2a                                                        ______________________________________                                                         KT.sub.50 (min.sec)                                          Test Compound      Northern house                                             (0.6% mosquito coil)                                                                             mosquito     Housefly                                      ______________________________________                                        The present compound                                                                          1      7'06"        8'00"                                     "              2       6'30"        7'42"                                     "              4       5'54"        7'00"                                     "              6       6'36"        7'24"                                     "              11      5'00"        6'36"                                     "              12      5'06"        6'24"                                     "              21      4'30"        5'00"                                     Allethrin              8'36"        17'00"                                    ______________________________________                                    

                  TABLE 2b                                                        ______________________________________                                                        KT.sub.50 (min.sec)                                            Test Compound    Northern house                                              (0.6% mosquito coil)                                                                            mosquito     Housefly                                       ______________________________________                                        The present compound 71                                                                         6'12"        7'00"                                          The present (d-cis,trans form)                                                                  3'48"        4'54"                                          The present (d-trans form)                                                                      4'12"        4'48"                                          The present compound 86                                                                         4'18"        5'30"                                          The present compound 89                                                                         4'30"        5'54"                                          The present compound 90                                                                         5'42"        5'06"                                          The present compound 91                                                                         5'18"        5'24"                                          The present compound 92                                                                         5'30"        5'00"                                          The present compound 126                                                                        4'00"        4'18"                                          Allethrin         8'24"        17'30"                                         ______________________________________                                    

TEXT EXAMPLE 2

The present compounds 1, 4, 5, 29, 68, 71, 79, 102, 109, 111, 126-130,142-144 and pyrethrin were respectively formulated into each oil sprayhaving each different concentration by use of deodorized kerosene. Each5 ml of the oil spray was sprayed by means of a Campbel's turn table[Soap and Sanitary Chemicals, Vol. 14, No. 6, 119 (1938)], and theshutter was opened on 20 seconds after the spraying.

A group of about 100 housefly adults was exposed to descending spray for10 minutes, thereafter was transferred to an observation case, was fed,and was allowed to stand at room temperature.

After a day, the dead and alive were counted to calculate the lethalratio.

The test was repeated several times, and the LC₅₀ value (lethalconcentration required for killing a half) obtained from the results isas shown in Tables 3a and 3b.

                  TABLE 3a                                                        ______________________________________                                        Test compound         LC.sub.50 (mg/100 ml)                                   ______________________________________                                        The present compound                                                                          68        400                                                 "               71        290                                                 "               79        83                                                  "               102       60                                                  "               109       34                                                  "               111       41                                                  "               142       120                                                 "               143       82                                                  "               144       29                                                  Pyrethrin I               210                                                 ______________________________________                                    

                  TABLE 3b                                                        ______________________________________                                        Test compound         LC.sub.50 (mg/100 ml)                                   ______________________________________                                        The present compound                                                                          1         550                                                 "               4         140                                                 "               5         240                                                 "               29        90                                                  "               126       30                                                  "               127       25                                                  "               128       90                                                  "               129       23                                                  The present compound                                                                          130       150                                                 Allethrin                 350                                                 ______________________________________                                    

In preparing the insecticidal compositions of the present invention, thepresent compounds may be formulated into oil sprays, emulsifiableconcentrates, dusts, aerosols, wettable powders, granules, mosquitocoils and other heating or non-heating fumigants according to theprocedures thoroughly known to those skilled in the art, using dilutingadjuvants for general insecticides like in the case of the conventionalpyrethroides. Alternatively, they may be formulated into death-inducingpower or solid preparations incorporated with baits or other substancesattractive for injurious insects.

Further, the present compounds can display more excellent insecticidalactivities when used in combination of 2 or more, and can be enhanced ininsecticidal effect when used in admixture with such synergists forpyrethroides asα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene(hereinafter referred to as "Piperonyl butoxide"),1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene (hereinafterreferred to as "Sulfoxide"),4-(3,4-methylenedioxyphenyl)-5-methyl-1,3-dioxane (hereinafter referredto as "Sufroxane"),N-(2-ethylhexyl)-bicyclo[2,2,1]hepta-5-ene-2,3-dicarboximide(hereinafter referred to as "MGK-264"), octachlorodipropyl ether(hereinafter referred to as "S-421") and isobornyl thiocyanoacetate(hereinafter referred to as "Thanite"), or with other known synergistseffective for allethrin and pyrethrin.

When phenol derivatives such as BHT, bisphenol derivatives, orarylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine andphenetidine-acetone condensates are added in suitable amounts asstabilizers, it is possible to obtain insecticidal compositions whichhave been more stabilized in effectiveness.

Furthermore, the present compounds may be used in admixture with otherphysiologically active materials, e.g. pyrethrin (pyrethrum extract),other known cyclopropanecarboxylic acid ester type insecticides such asallethrin, N-(chrysanthemoxymethyl)-3,4,5,6-tetrahydrophthalimide(hereinafter referred to as "Tetramethrin"), 5-benzyl-3-furylmethylchrysanthemate (hereinafter referred to as "resmethrin") and geometricalor optical isomers thereof, organo-chlorine type insecticides such asDDT, BHC and methoxychlor, organo-phosphorus type insecticides such asO,O-dimethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate (hereinafterreferred to as "fenitrothion"),O,O-dimethyl-O-(2,2-dichlorovinyl)-phosphate (hereinafter referred to asDDVP), O,O-dimethyl-O-(3-methyl-4-methylmercaptophenyl)phosphorothioate(trademark: Baycid),O,O-diethyl-O-1-(2',4'-dichlorophenyl)-2-chloro-vinyl phosphate(trademark: Vinyphate),O,O-dimethyl-S-[1,2-bis(ethoxycarbonyl)ethyl]phosphorodithioate(trademark: Malathion),2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide (trademark:Salithion), ethyl-dimethyldithiophosphorylphenyl acetate (trademark:Papthion), O,O-dimethyl-p-cyanophenyl thiophosphate (trademark: Cyanox),O,O-dimethyl-1-hydroxy-2,2,2-trichloroethyl phosphonate (trademark:Dipterex), and 2-isopropyl-4-methylpyrimidyl-6-diethyl-thiophosphate(trademark: Diazinon), carbamate type insecticides such as1-naphthyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate,3,5-dimethylphenyl-N-methylcarbamate,2-isopropoxyphenyl-N-methylcarbamate (trademark: Suncide), andS-methyl-N-[(methylcarbamoyl)oxy]thioacetimidate (trademark: Lannate),such insecticides as N'-(2-methyl-4-chlorophenyl)-N,N-dimethylformamidine (trademark: Galecron) and1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride(trademark: Cartap) or with other agricultural chemicals such asfungicides, nematocides, acaricides, herbicides, fertilizers, etc.,whereby multi-purpose compositions excellent in effectiveness can beprepared, and synergistic effects due to blending therewith may beexpected.

The present invention will be explained in more detail with reference tothe following examples which are only illustrative, and not limitative.

Preparation of the insecticidal composition containing acyclopropanecarboxylate [I]:

EXAMPLE A

The cyclopropanecarboxylate [I] (Compound No. 2, 4, 5, 14, 16, 20, 21,24, 28, 71, 72, 90, 91, 92, 93, 94, 102, 103, 106, 110, 114, 120, 121,126-130, 131-139, 142-144) (0.2 part by weight) was dissolved inkerosene (99.8 parts by weight) to make an oil preparation.

EXAMPLE B

The cyclopropanecarboxylate [I] (Compound No. 31-63) (1 part by weight)was dissolved in kerosene (99 parts by weight) to make an oilpreparation.

EXAMPLE C

The cyclopropanecarboxylate [I] (Compound No. 10, 11, 13, 15, 19, 22,23, 25, 102-125) (0.5 part by weight) was dissolved in kerosene (99.5parts by weight) to make an oil spray.

EXAMPLE D

The cyclopropanecarboxylate [I] (Compound No. 1-5, 7, 9, 10-12, 14,16-18, 20-26, 28, 71, 72, 86, 89, 94, 95, 102-106, 110-112, 121 122)(0.1 part by weight) and piperonyl butoxide (0.5 part by weight) weredissolved in kerosene (99.4 parts by weight) to make an oil preparation.

EXAMPLE E

The cyclopropanecarboxylate [I] (Compound No. 31-37, 39, 40-42, 44-48,50-52, 54, 62) (0.3 part by weight) and piperonyl butoxide (1.5 parts byweight) were dissolved in kerosene (98.2 parts by weight) to make an oilpreparation.

EXAMPLE F

The cyclopropanecarboxylate [I] (Compound No. 1-5, 8, 16, 27, 31-33, 36,37, 102-106, 109, 116, 117, 126-130) (0.1 part by weight) and DDVP (0.2part by weight) were dissolved in kerosene (99.7 parts by weight) tomake an oil preparation.

EXAMPLE G

The cyclopropanecarboxylate [I] (Compound No. 67-70, 76-83, 98-101) (0.2part by weight) and DDVP (0.2 part by weight) were dissolved in kerosene(99.6 parts by weight) to make an oil preparation.

EXAMPLE H

The cyclopropanecarboxylate [I] (Compound No. 1-4, 16, 20, 28, 71, 72,90, 91, 92, 94, 95, 126-130, 102-125, 142-144) (10 parts by weight),S-421 (20 parts by weight), a surface active agent ("Sorpol SM-200",manufactured by Toho Kagaku Co., Ltd.) (15 parts by weight) and xylene(55 parts by weight) were mixed together to make an emulsionpreparation.

EXAMPLE I

The cyclopropanecarboxylate [I] (Compound No. 31-33, 46, 50, 53, 131,132, 135-140) (5 parts by weight), Sufroxan (15 parts by weight), asurface active agent ("Sorpol SM-200", manufactured by Toho Kagaku Co.,Ltd.) (10 parts by weight) and xylene (70 parts by weight) were mixedtogether to make an emulsion preparation.

EXAMPLE J

To the cyclopropanecarboxylate [I] (Compound No. 2, 31, 71, 102, 109,120) (0.4 part by weight), Chrysron (trademark of Sumitomo ChemicalCompany, Limited) (0.2 part by weight) was added. The resultant mixturewas admixed with xylene (7 parts by weight) and deoderized kerosene (7.4parts by weight) and charged into an aerosol vessel. The vessel wasprovided with a valve means, and an atomizer (liquefied petroleum gas)(85 parts by weight) was charged into the vessel through the said valvemeans to make an aerosol preparation.

EXAMPLE K

The cyclopropanecarboxylate [I] (Compound No. 4, 39, d-transchrysanthemic acid ester of 71, 111 126-130) (0.4 part by weight),piperonyl butoxide (2.0 parts by weight), xylene (6.2 parts by weight)and deoderized kerosene (7.0 parts by weight) were mixed together andcharged into an aerosol vessel as in Example J to make an aerosolpreparation.

EXAMPLE L

The cyclopropanecarboxylate [I] (Compound No. 21, 40, 94, 104, 122, 131,132, 135-140) (0.3 part by weight), Chrysron (0.1 part by weight),Thanite (2.0 parts by weight), xylene (6 parts by weight) and deoderizedkerosene (6.6 parts by weight) were mixed together and charged into anaerosol vessel as in Example J to make an aerosol preparation.

EXAMPLE M

The cyclopropanecarboxylate [I] (Compound No. 94, 109, d-transchrysanthemic acid ester of 2, 32) (0.2 part by weight), tetrahethrin(0.2 part by weight), piperonyl butoxide (2 parts by weight), xylene (6parts by weight) and deoderized kerosene (6.6 parts by weight) weremixed together and charged into an aerosol vessel as in Example J tomake an aerosol preparation.

EXAMPLE N

The cyclopropanecarboxylate [I] (Compound No. 11, 46, 92, 110, 121) (0.4part by weight), Fenitrothion (0.5 part by weight), xylene (7 parts byweight) and deoderized kerosene (7.1 parts by weight) were mixedtogether and charged into an aerosol vessel as in Example J to make anaerosol preparation.

EXAMPLE O

The cyclopropanecarboxylate [I] (Compound No. 111, d-trans chrysanthemicacid ester of 4, 71, d-cis-chrysanthemic acid ester of 31, 38, 46) (0.4part by weight), piperonyl butoxide (2 parts by weight), deoderizedkerosene (11.6 parts by weight) and an emulsifier ("Atmos 300";manufactured by Atlas Chemical Co., Ltd.) (1 part by weight) were mixedtogether, and water (50 parts by weight) was added thereto. Theresulting emulsion was charged with a 3:1 mixture of deodorized butaneand deoderized propane (35 parts by weight) into an aerosol vessel tomake a water-base aerosol preparation.

EXAMPLE P

The cyclopropanecarboxylate [I] (Compound No. each d-cis form of (1, 2,4, 5, 11-13, 20-24, 71, 72), 102, 103, 105, 106, 112-114, 116, 117, 123)(0.5 g) was dissolved in methanol (20 ml), and the resultant solutionwas admixed uniformly with a carrier for mosquito coil consisting ofPyrethrum marc., Tabu powder and wood powder in a weight ratio of 5:3:1(99.5 g). After evaporation of methanol, the residue was kneaded wellwith water (150 ml), shaped and dried to make a mosquito coil.

EXAMPLE Q

The cyclopropanecarboxylate [I] (Compound No. d-cis form of 31, 37, 46)(0.8 g) was dissolved in methanol (20 ml), and the resultant solutionwas admixed uniformly with a carrier for mosquito coil consisting ofPyrethrum marc., Tobu powder and wood powder in a weight ratio of 5:3:1(99.2 g). After evaporation of methanol, the residue was kneaded wellwith water (150 ml), shaped and dried to make a mosquito coil.

EXAMPLE R

The cyclopropanecarboxylate [I] (Compound No. 1, 2, 4, 11, 12, 21, 27,31, 64, 65, 71-75, 86, 90, 102, 103, 105, 111, 112, 116, 122) (0.3 g)and allethrin (0.3 g) were dissolved in methanol (20 ml), and theresulting solution was treated as in Example P to make a mosquito coil.

EXAMPLE S

A sheet of asbestos of 2.5 cm in length, 1.5 cm in width and 0.3 mm inthickness was dipped in a solution of the cyclopropanecarboxylate [I](Compound No. 102, 109, d-trans form of (4) (0.05 g) in chloroform tomake an insecticidal fumigant preparation which was used by heating on ahot plate.

As a fibrous carrier, a pulp plate with the same effects as asbestos maybe used.

EXAMPLE T

A sheet of asbestos of 3.5 cm in length, 1.5 cm in width and 0.3 mm inthickness was dipped in a solution of the cyclopropanecarboxylate [I](Compound No. 2, 4, 5, 11, 12, 21, 65, 71, 72, 86, 89-91, 102, 105, 109,111, 116) (0.1 g), d-trans allethrin (0.02 g), BHT (0.05 g) andpiperonyl butoxide (0.1 g) in chloroform to make an insecticidalfumigant preparation which was used by heating on a hot plate. As afibrous carrier, a pulp plate with the same effects as asbestos may beused.

EXAMPLE U

The cyclopropanecarboxylate [I] (Compound No. 24, 28, 94, 95, 102, 109,111, d-trans form of 2, 4, 71, 72) (1 part by weight), Safroxane (3parts by weight), acetone (20 parts by weight) and 300 mesh diatomaceousearth (96 parts by weight) were mixed well and the acetone wasevaporated therefrom make a dust preparation.

EXAMPLE V

The cyclopropanecarboxylate [I] (Compound No. 16, 31, 71, 103, 106, 116,122) (20 parts by weight), 1-naphthyl-N-methylcarbamate (5 parts byweight), an emulsifier ("Sorpol SM-200") (5 parts by weight) and 300mesh talc (70 parts by weight) were mixed well to make a wettable powderpreparation.

EXAMPLE W

The cyclopropanecarboxylate [I] (Compound No. 4, 31, 32, 96, 102, 111,114, 122) (3 parts by weight), 5-propargylfurfuryl chrysanthemate (2parts by weight), sodium ligninsulfonate ("Toyolignin CT"; manufacturedby Toyo Boseki Kabushiki Kaisha) (5 parts by weight) and clay ("GSMclay"; manufactured by Zieclite Kogyo Co., Ltd.) (90 parts by weight)were mixed well.

The resulting mixture was admixed with 10% by weight of water, granuledand dried to give a granule preparation.

EXAMPLE X

The cyclopropanecarboxylate [I] (Compound No. 1-28, 31-35, 39-43, 45-48,50, 53-63, 64-98, 131-141, 102-125, 142-144) (20 parts by weight), anemulsifier ("Sorpol SM-200") (20 parts by weight) and xylene (60 partsby weight) were mixed well to make an emulsion preparation.

EXAMPLE Y

The cyclopropanecarboxylic [I] (Compound No. 2, 4, 12, 21, 64, 65, 67,71-75, 86, 89, 93, 101, 110, 120) (0.05 g),5-propargyl-2-methyl-3-furylmethyl chrysanthemate (0.02 g), BHT (0.2 g),piperonyl butoxide (0.05 g) were mixed to make an insecticidal fumigantpreparation according to Example S which was used by heating on a hotplate.

Insecticidal effect of the insecticidal composition containing thecyclopropanecarboxylate [I] is as follows:

EXAMPLE I

The oil preparation obtained as in Example A, C, D, F or G (5 ml) wassprayed by the use of a Campbell's turn table [Soap & SanitaryChemicals, Vol. 14, No. 6, 119 (1938)] on 100 adults of housefly, andthe houseflies were exposed under the spray for 10 minutes. Thehouseflies were then allowed to stand with feeding. On the next day, thedeath of more than 80% was confirmed.

EXAMPLE II

In a glass chamber of 70 cm cube, 50 adults of mosquito were released.0.7 Millilieters of the oil preparation obtained as in Example F wassprayed with the glass atomizer at a pressure of 20 pounds and within 10minutes thereafter more than 80% of the mosquitos were knocked down. Onthe next day, the death of more than 80% was confirmed for each oilpreparation.

EXAMPLE III

The emulsion preparation obtained as in Example H was diuted with waterto make a 10,000 fold dilution. The dilution (2 liters) was charged in acase of 23 cm in length, 30 cm in width and 6 cm in depth, and 100larvae of mosquito were released therein. On the next day, the death ofmore than 90% was confirmed.

EXAMPLE IV

In a glass chamber of 70 cm cube, 50 adults of mosquito were released. Asmall electric fan of 13 cm in diameter equipped in the chamber wasdriven, and the mosquito coil obtained as in Example P or R (0.1 g) wasignited at both ends and placed therein. More than 80% of the mosquitoswas knocked down within 20 minutes. One the next day, the death of morethan 80% was confirmed.

EXAMPLE V

In a glass chamber of 70 cm cube, 50 adults of mosquitos were released.A small electric fan of 13 cm in diameter equipped in the chamber wasdriven, and the fumigant prparation obtained as in Example S, T or Y wasplaced on a hot plate threin. More than 80% of the mosquitos was knockeddown within 20 minutes.

EXAMPLE VI

The insecticidal potency of the aerosol preparation obtained as inExample J, K, L, M, N or O against adults of housefly was testedaccording to the aerosol test method using Peet Grady chamber (6 feet)³as described in Soap & Chemical Specialities Bluebook (1965). More than80% of houseflies were knocked down within 15 minutes after spraying. Onthe next day, the death of more than 70% was confirmed.

EXAMPLE VII

The dust preparation obtained as in Example U was uniformly dispersed ona petri dish of 14 cm in diameter to make a layer in the rate of 2 g/m²on the bottom. On the wall of the petri dish, butter was appliedremaining about 1 cm from the bottom. Ten aduluts of cockroach werereleased therein and contacted with the petri dish for 30 minutes. Threedays after the contact, more than 70% of the cockroaches were dead.

EXAMPLE VIII

The emulsion preparation obtained as in Example X was diluted with waterto make a 100 fold dilution. The dilution (10 ml) was sprayed on riceplants cultivated for 45 days after seeding in a 1/50,000 Wagner pot.Then, the pot was covered with a net, and 30 adults of green riceleafhoppr were released therein. After one day, more than 70% of thegreen rice leafhoppers were killed.

EXAMPLE IX

About 20 rice seedlings, cultivated for 20 days after sowing in a flowerpot of 8.5 cm in diameter, were sprayed with each of the emulsifiableconcentrates and wettable powder obtained in Examples H, V or X whichwere diluted to 200 times with water. After air-drying, each pot wascovered with a wire cage, and 30 adults of planthoppers were releasedtherein. The observation was made after 24 hrs. As a result, more than80% of planthoppers were dead in each case.

EXAMPLE X

Ten of the 3rd or 4th instar larvae of tobacco cut worm were put into apetri dish of 17 cm in diameter.

One ml of the present compound (4, 11, 28, 92, 94, 95, 109, 111) in formof an emulsion obtained in Example X, which were diluted to 50 timeswith water, were sprayed by means of a settling tower. The said larvaewere removed into another petri dish with the leaves of the chinesecabbage leaves. Observation was made after 48 hrs. As a result, morethan 90% of the larvae were dead in each case.

EXAMPLE XI

One gram of the granular composition obtained as in Example W was putinto 10 l of water in a 14 l pail made of polyethylene. After one day,about 100 fullgrown larvae of Northern house mosquito were released intothe said water. In 24 hrs., more than 90% of the mosquito larvae weredead.

EXAMPLE XII

Mottled kidney bean plants at 2 leaves-stage, which had elapsed 9 daysafter sowing, were parasitized with 10 to 15 carmine mites per leaf, andleft in a room at 27° C. for a week.

Then each of the emulsifiable concentrate obtained as in Example X werediluted to 500 times with water and the dilutions were sprayed with 10ml per pot on the turn table.

The observation was made after 10 days. As a result, the increaseddamage of the said plant was not found in each case.

EXAMPLE XIII

Rice plants at the tillering stage were grown in Wagner pots, and thedepth of water was kept at 5 cm.

The present compound (4) obtained in Example W was put into the Wagnerpot with 10 kg/10 ares, and the said pot was covered with a wire cageinto which 20 adult leafhoppers were released.

As a result, more than 90% of leafhoppers were dead after 24 hrs.

EXAMPLE XIV

In the vinyl house, the Chinese cabbages were cultivated and the leaveswere parasitized with the larvae of tobacco cut worm, diamondback mothand common cabbage worms.

The vinyl house (its height was 2 m) was divided into compartments of 30m² in area and 10 grams of the present compound (1, 4) in the form of40% wettable powder was put into the plate heated by fire.

As a result, the increasing of the damage was not found in each case.

EXAMPLE XV

About 20 rice seedlings, cultivated for 20 days aftr sowing in a flowerpot of 8.5 cm in diameter, were sprayed with each of the emulsifiableconcentrates obtained as in Example X which were diluted to 400 timeswith water. After air-drying, each pot was covered with a wire cage,into which 20 adult planthoppers were released as time elapsed. And theobservation was made after 24 hours.

The results obtained are as shown in the following Table 4.

                  TABLE 4                                                         ______________________________________                                                      Mortality (%)                                                   Test compound   After 1 day After 6 days                                      ______________________________________                                        31              100         75.8                                              32              100         100                                               39              100         85.0                                              40              100         66.7                                              62              100         100                                               63              100         53.3                                              Meobal          100         40.0                                              ______________________________________                                         Meobal: 3,4Dimethylphenyl-N-methylcarbamate                              

EXAMPLE XVI

About 20 rice seedlings, cultivated for 20 days after sowing in a flowerpot of 8.5 cm in diameter were sprayed with each of the presentcompounds (31, 35, 39, 40, 42, 45, 48, 55, 59, 60, 63, 131-134, 139) inthe form of an emulsion which were diluted to 50 times. Each pot was putinto the beaker and covered with gauze, into which leafhoppers ofresistant and susceptible strains, respectively, were released in eachbeaker. And the number of knocked down insects after 1 hour and themortality after 24 hours were counted. As a result, the knock downpercentage was more than 50% and the mortality was more than 80% in eachcase.

EXAMPLE XVII

Each of the emulsifiable concentrates obtained in Example X was dilutedto 100 times their volume with water.

The resulting solution was sprayed to potted Chinese cabbages at their5-6 leaf stage in a proportion of 10 ml per pot.

After air-drying, 4th. instar larvae of diamondback moths wereparasitized on the leaves. After 24 hours, more than 80% of the larvaewere dead in each case.

EXAMPLE XVIII

Each 5% dust of the present compounds 31, 32, 62, 63 was spread in aratio of 3 kg/10 ares on the Chinese cabbages of 40 days after sowing inthe field. And about 9,000 eggs of tobacco cut worm were put on theleaves of the Chinese cabbages per 10 ares every 5 days for a month.

As a result, the damage of the Chinese cabbages by tobacco cut worms wasnot found in the field of the Chinese cabbages for 2 months.

EXAMPLE XIX

30 Full grown larvae of the Northern house mosquito were released intothe beaker with 200 ml of dilution of each emulsifiable concentrateswhich obtained in Example X.

After 24 hours, the death and alive were observed to culculate LC₅₀.

The results obtained are as shown in the following Table 5

                  TABLE 5                                                         ______________________________________                                        Test compound     Value of LC.sub.50 (ppm)                                    ______________________________________                                        31                0.12                                                        32                0.069                                                       33                0.34                                                        34                0.14                                                        62                0.034                                                       63                0.14                                                        ______________________________________                                    

EXAMPLE XX

The oil preparatin obtained as in Example B (5 ml) was sprayed by theuse of a Campbell's turn table [Soap & Sanitary Chemicals, Vol. 14, No.6, 119 (1938)] on 100 adults of houseflies were exposed to the spray for10 minutes. The houseflies were then allowed to stand with feeding. Onthe next day, dead and alive were observed.

The results obtained are as shown in the following Table

                  TABLE 6                                                         ______________________________________                                        Test compound       Mortality (%)                                             ______________________________________                                        31                  92                                                        32                  96                                                        62                  93                                                        63                  95                                                        136                 90                                                        137                 100                                                       138                 100                                                       139                 95                                                        ______________________________________                                    

EXAMPLE XXI

An emulsion prepared by diluting with water the present compounds 31,32, 33, 34, 35, 46, 63, in the form of an emulsifiable concentrate wasorally administrated to male mice of about 20 g in body weight. From thealive and dead of the mice during 48 hours, LD₅₀ value was calculated.The results obtained are shown in the following Table.

                  TABLE 7                                                         ______________________________________                                        Test compound        LD.sub.50 mg/kg                                          ______________________________________                                        31                   >500                                                     32                   >500                                                     33                   >600                                                     34                   >600                                                     35                   >600                                                     46                   >600                                                     63                   >600                                                     ______________________________________                                    

EXAMPLE XXII

The oil preparation of the present compounds 31, 62, 131, 132, 133, 134,135, 139, obtained as in Example A having different concentrations weresprayed by the use of a Campbelle's turn table [Soap & SanitaryChemicals, Vol. 14, No. 6, 119 (1938)] on 100 adults of houseflies wereexposed to the spray for 10 minutes. The houseflies were then allowed tostand with feeding. On the next day, dead and alive were counted toculculate LD₅₀.

The results obtained are as shown in the following table.

                  TABLE 8                                                         ______________________________________                                        Test Compound      LD.sub.50 (mg/100 ml)                                      ______________________________________                                        31                 250                                                        62                 210                                                        131                52                                                         132                32                                                         133                50                                                         134                100                                                        135                98                                                         139                86                                                         Allethrin          350                                                        ______________________________________                                    

What is claimed is:
 1. A compound of the formula, ##STR163## wherein R₁represents lower alkenyl having up to 5 carbon atoms, or lower alkynylhaving up to 5 carbon atoms; R₂ and R₃ individually represent hydrogen,lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5carbon atoms, or lower alkynyl having up to 5 carbon atoms; R₆represents hydrogen or methyl;and A is hydroxy.
 2. A compound accordingto claim 1 which is 1-ethynyl-2-methyl-3-propargylallyl alcohol.
 3. Acompound according to claim 1, having the formula ##STR164##
 4. Acompound according to claim 1, having the formula ##STR165##
 5. Acompound according to claim 1, having the formula ##STR166##
 6. Acompound according to claim 1, having the formula ##STR167##
 7. Acompound having the formula ##STR168##
 8. A compound having the formula##STR169##